Aminosilane Initiators And Functionalized Polymers Prepared Therefrom

ABSTRACT

Metallated aminosilane compounds for use as functional initiators in anionic polymerizations and processes for producing an aminosilane-functionalized polymer using the metallated aminosilane compounds to initiate anionic polymerization of at least one type of anionically polymerizable monomer. Preferred use of the metallated aminosilane compounds results in rubber compositions for use in tires comprising an aminosilane functionalized polymer. A telechelic polymer may result from use of the metallated aminosilane compound as a functional terminator.

This application claims priority to U.S. Provisional Application No.61/428,253, filed on Dec. 30, 2010, which is hereby incorporated byreference in its entirety.

FIELD OF INVENTION

The present application relates to silane-functionalized polymers andrubber vulcanizates prepared therefrom.

BACKGROUND

In the art of making tires, it can be desirable to employ rubbervulcanizates that demonstrate reduced hysteresis loss, i.e., less lossof mechanical energy to heat. Hysteresis loss is often attributed topolymer free ends within the cross-linked rubber network, as well as thedisassociation of filler agglomerates.

Functionalized polymers have been employed to reduce hysteresis loss andincrease bound rubber. The functional group of the functionalizedpolymer is believed to reduce the number of polymer free ends. Also, theinteraction between the functional group and the filler particlesreduces filler agglomeration, which thereby reduces hysteretic lossesattributable to the disassociation of filler agglomerates. The presentapplication stems from a recognition that an aminosilane (“silazane”)functional group within the polymer portion of a rubber vulcanizate hasbeen found to improve the physical properties of the rubber vulcanizate.The aminosilane functionality in the polymer presumably improves theinteraction of the polymer with additional components, such as silicafillers. This improved interaction often translates into improved mixingand better dispersion of ingredients.

SUMMARY

The present application provides metallated aminosilane compounds forinitiating anionic polymerizations.

The present application also provides processes for producing anaminosilane-functionalized polymer comprising the steps of providing aninitiator by preparing a metallated aminosilane compound, eitherpre-formed or in situ, and polymerizing at least one type of anionicallypolymerizable monomer using the metallated aminosilane compound toinitiate the polymerization.

The present application also provides a telechelic polymer having afunctionalized head group and a functionalized tail group, made by amethod comprising initiating polymerization of at least one type ofanionically polymerizable monomer by using a metallated aminosilanecompound.

The present application also provides a rubber composition for use intires comprising an aminosilane functionalized polymer that has beenmade according to the processes disclosed herein.

The present application further provides a polymer compositioncomprising an elastomeric polymer meeting formula (IV) and havingaminosilane-functionalized chain ends.

DETAILED DESCRIPTION

This application provides functionalized initiators in the form ofparticular metallated aminosilane compounds useful for anionicpolymerization. Polymers prepared using these initiators contain afunctional group at the head of the polymer chain, and it has beendiscovered that vulcanizable elastomeric compounds and articles thereofbased upon such functional polymers exhibit useful properties. Ingeneral, the “head” of a polymer is the chain end where initiatorresidue resides, whereas the “tail” is the chain end nearest thelocation where the final monomer unit has been added to the polymer. Asused herein, the term “at the head” and “at the tail” mean locations ator near the head and tail, respectively.

Use of the metallated aminosilane compounds disclosed herein to initiateanionic addition polymerization (or copolymerization) allows for theproduction of aminosilane-functionalized polymers having the silicon ofthe aminosilane group directly bonded to the end of a polymer chainthrough one or more carbon atoms. Directly bonding the silicon of theaminosilane to the head of the polymer chain through one or more carbonbonds allows for an increased likelihood that silicon will remain boundto the polymer chain throughout the polymerization reaction and anysubsequent processing of the polymer with rubber vulcanizate materials.Without wishing to be bound by theory, it is believed that theaminosilane-functional polymer may react by hydrolysis and condense withfillers in rubber vulcanizate compounds to give improved fillermicrodispersion, resulting in reduced hysteresis rubber vulcanizatecompounds that are useful in improving fuel economy of tires madetherefrom.

In one embodiment, the present application discloses a metallatedaminosilane compound for initiating an anionic polymerization comprisingthe reaction product of at least one metallating agent, and at least onealkenylaminosilane compound having the formula

where n is a whole number selected from the group consisting of 0-2, andm is a whole number selected from the group consisting of 1-3, with theproviso that the sum of m and n equals 3; where each R is independentlya hydrogen, alkyl or aryl group; where each R¹ is independently ahydrocarbyl group; where each R² is independently a hydrocarbyl grouphaving between 2 and 12 carbon atoms; where each R³ is independently ahydrocarbylene group having between 2 and 12 carbon atoms; and where oneor more R² may form a bridge between two nitrogen atoms when m isgreater than 1.

In another embodiment, the present application discloses a metallatedaminosilane compound for initiating an anionic polymerization comprisingthe reaction product of at least one metallating agent and at least onealkylaminosilane compound having the formula

where n is a whole number selected from the group consisting of 0-2, andm is a whole number selected from the group consisting of 1-3, with theproviso that the sum of m and n equals 3; where T is a methyl, ethyl,propyl, or allylic group; where each R⁴ and R⁵ is independently ahydrocarbyl group; where each R⁶ is independently a hydrocarbylene; andwhere one or more R⁵ may form a bridge between two nitrogen atoms when mis greater than 1.

In general, the aminosilane compounds of the present application may beany compound that contains between one and three dihydrocarbylaminogroups bonded directly to a silicon atom. The aminosilane compounds maycontain various other hydrocarbyl or phenyl groups in addition todihydrocarbylamino groups.

Alkenylaminosilane compounds described in the present application areaminosilane compounds that include a branched or unbranched alkenylgroup

bonded to the silicon atom. The alkenyl group may contain one or moresubstituents (A). In general, the alkenyl group is selected such thatthe metallating agent will add across the unsaturation, and preferably,each substituent (A) is independently a hydrogen, an alkyl or an arylgroup. Typical alkyl groups include methyl, ethyl, propyl, isopropyl,n-butyl, and t-butyl. Typical aryl groups include phenyl. Preferably,the alkenyl group is etheneyl (i.e., A is hydrogen).

In one embodiment, the alkenylaminosilane is selected from the groupconsisting of alkyleneiminoalkenyldimethylsilane,bis-(alkyleneimino)alkenylmethylsilane,tris-(alkyleneimino)alkenylsilane, aryleneiminoalkenyldimethylsilane,bis-(aryleneimino)alkenylmethylsilane, tris-(aryleneimino)alkenylsilane,diarylaminoalkenyldimethylsilane, bis-(diarylamino)alkenylmethylsilane,tris-(diarylamino)alkenylaminosilane, and combinations thereof.Preferably, the alkenylaminosilane compound is selected from the groupconsisting of hexamethyleneiminoalkenyldimethylsilane,bis-(hexamethyleneimino)alkenylmethylsilane,tris-(hexamethyleneimino)alkenylsilane,diphenylaminoalkenyldimethylsilane,bis-(diphenylamino)alkenylmethylsilane,tris-(diphenylamino)alkenylaminosilane,diisobutylaminoalkenyldimethylsilane,bis-(diisobutylamino)alkenylmethylsilane,tris-(diisobutylamino)alkenylsilane, and combinations thereof.

In another embodiment, the alkenylaminosilane compound is selected fromthe group consisting of alkyleneiminoethenyldimethylsilane,bis-(alkyleneimino)ethenylmethylsilane,tris-(alkyleneimino)ethenylsilane, aryleneiminoethenyldimethylsilane,bis-(aryleneimino)ethenylmethylsilane, tris-(aryleneimino)ethenylsilane,diarylaminoethenyldimethylsilane, bis-(diarylamino)ethenylmethylsilane,tris-(diarylamino)ethenylaminosilane, and combinations thereof.Preferably, the alkenylaminosilane compound is selected from the groupconsisting of hexamethyleneiminoethenyldimethylsilane,bis-(hexamethyleneimino)ethenylmethylsilane,tris-(hexamethyleneimino)ethenylsilane,diphenylaminoethenyldimethylsilane,bis-(diphenylamino)ethenylmethylsilane,tris-(diphenylamino)ethenylaminosilane,diisobutylaminoethenyldimethylsilane,bis-(diisobutylamino)ethenylmethylsilane,tris-(diisobutylamino)ethenylsilane, and combinations thereof. It isspecifically contemplated that other alkenylaminosilane compounds can beutilized.

Alkylaminosilane compounds described in the present application areaminosilane compounds that have at least one alkyl or allylic group (“T”or “tether” group) directly bonded to the silicon atom. As used herein,the term “allylic group” refers to any substituted or unsubstitutedallylic group

bonded to the silicon atom. The allylic group may contain one or morehydrogen, alkyl or aryl substituents (B). In general, T is selected in amanner such that the metallating reagent may abstract a proton and themetal-alkyl bond generated initiates polymerization. Non-limitingexamples of T are methyl, ethyl, propyl and allyl groups.

In one embodiment, the alkylaminosilane compound is selected from thegroup consisting of alkyleneiminodihydrocarbylalkylsilane,bis-(alkyleneimino)hydrocarbylalkylsilane,tris-(alkyleneimino)alkylsilane, aryleneiminodihydrocarbylalkylsilane,bis-(aryleneimino)hydrocarbylalkylsilane,tris-(aryleneimino)alkylsilane, dialkylaminodihydrocarbylalkylsilane,bis-(dialkylamino)hydrocarbylalkylsilane,tris-(dialkylamino)alkylsilane, diarylaminodihydrocarbylalkylsilane,bis-(diarylamino)hydrocarbylalkylsilane, tris-(diarylamino)alkylsilane,and combinations thereof. In another embodiment, the alkylaminosilanecompound is selected from the group consisting ofalkyleneiminodihydrocarbylallylsilane,bis-(alkyleneimino)hydrocarbylallylsilane,tris-(alkyleneimino)allylsilane, aryleneiminodihydrocarbylallylsilane,bis-(aryleneimino)hydrocarbylallylsilane,tris-(aryleneimino)allylsilane, dialkylaminodihydrocarbylallylsilane,bis-(dialkylamino)hydrocarbylallylsilane,tris-(dialkylamino)allylsilane, diarylaminodihydrocarbylallylsilane,bis-(diarylamino)hydrocarbylallylsilane, tris-(diarylamino)allylsilane,and combinations thereof. Preferably, the alkylaminosilane compound isselected from the group consisting ofbis-(dialkylamino)phenylmethylsilane,bis-(hexamethyleneimino)phenylmethylsilane,tris-(dialkylamino)allylsilane, and combinations thereof. It isspecifically contemplated that other alkylaminosilane compounds can beutilized.

Metallation, as is well-known in the art, typically involves a processwhere a proton of an organic compound is replaced with a metal. Themetal is usually derived from an organometallic compound. Metallating anaminosilane compound to form an initiator, as described herein, may beaccomplished in various ways.

Generally, in the context of alkenylaminosilane compounds, themetallating agent is any compound capable of metallating analkenylaminosilane. Without wishing to be bound by any particulartheory, in the context of alkenylaminosilane compounds, the organicmoeity undergoing metallation is the alkenyl group attached to thesilicon of the aminosilane compound. In this context, instead ofreplacing a proton, the metallating agent compound effectively addsacross the alkenyl pi-bond.

Generally, in the context of alkylaminosilane compounds, the metallatingagent is any compound capable of metallating an alkylaminosilane. Unlikemetallating an alkenylaminosilane compound, however, in the context ofalkylaminosilane compounds, the metallating agent operates bydeprotonating an organic substituent of the aminosilane—typically thealkyl or allylic tether group T. Metallation via deprotonation mayrequire a more highly basic solution than that required by a metallationvia addition, discussed above. In this regard, deprotonation may beencouraged by appropriate selection of metallating agent. For example,the use of sec- or tert-butyl lithium typically encourages metallationof an alkylaminosilane compound. In addition, deprotonation may beencouraged through the use of a metallating agent in conjunction with aLewis base. Non-limiting examples of organic Lewis bases include ethers,amines, phosphines, sulfoxides, phosphoramides, and Grignard reagents. Amixture of any of these (or others) may be used.

In another embodiment, deprotonation may be encouraged through the useof a metallating agent in conjunction with a reagent selected from thegroup consisting of alkali metal alkoxide (e.g., Lochmann's base),alkali metal arylsulfonate, and combinations thereof.

Non-limiting examples of metallating agents include organometalliccompounds such as hydrocarbyl lithium compounds, hydrocarbyl sodiumcompounds, hydrocarbyl potassium compounds, hydrocarbyl magnesiumcompounds, and combinations thereof. Preferably, the metallating agentis a hydrocarbyl lithium or hydrocarbyl sodium compound, or combinationsthereof. Typically, the metallating agent is a hydrocarbyl lithiumcompound having the general formula C—Li, where C is selected from thegroup consisting of alkyls, cycloalkyls, alkenyls, aryls, and aralkylshaving from 1 to 20 carbon atoms. Typical alkyls include but are notlimited to isopropyl, butyl isomers, and pentyl isomers.

The metallated aminosilane initiator may optionally be pre-formed bypre-mixing the metallating agent and the alkylaminosilane oralkenylaminosilane compound (collectively, “ingredients”) in the absenceof the monomer to be polymerized, at an appropriate temperature(generally between −20° C. to 80° C.), and the resulting reactionproduct may be aged for a period of time ranging from a few seconds to afew days and then mixed with the monomer solution. If a Lewis base orother basic reagent is utilized, it may also be added to the mixture atthis point. In pre-forming the initiator, an organic solvent or carriermay be employed, where it may serve to dissolve the ingredients.Alternatively, the solvent may simply serve as a carrier. Any organicsolvent utilized is preferably inert to the metallated aminosilanecompound and other ingredients. Useful solvents include polar andnon-polar hydrocarbon solvents such as aromatic hydrocarbons, aliphatichydrocarbons, and cycloaliphatic hydrocarbons. Mixtures of suchhydrocarbons may also be used.

With regard to alkenylaminosilanes, in another embodiment, themetallated alkenylaminosilane initiator may optionally be formed insitu. Generally, the in situ preparation of anionic initiator ispracticed by creating a solution comprising a polymerization solvent, ifany, and one or more of the monomer(s) to be polymerized, and by mixingthe alkenylaminosilane compound and metallating agent with the solution.Process conditions are adjusted so as to allow for the formation of asolution (cement) containing the desired functional polymer. Processconditions, such as reaction time and temperature may vary as necessaryto allow the alkenylaminosilane compound and metallating agent to react,and subsequently polymerize the monomer solution.

In one embodiment of the present application, a process for producing anaminosilane-functionalized polymer comprises the steps of: (a) providinga pre-formed anionic initiator by preparing a metallated aminosilanecompound comprising the reaction product of at least one metallatingagent and at least one compound having formula (IA), (IB), (IIA) or(IIB), and (b) polymerizing at least one type of anionicallypolymerizable monomer by using the metallated aminosilane compound toinitiate the polymerization.

In another embodiment of the present application, a process forproducing an aminosilane-functionalized polymer comprises the steps of:(a) providing an initiator formed in situ by mixing at least one type ofanionically polymerizable monomer with at least one alkenylaminosilanecompound having the formula (IA) or (IB), and (b) adding at least onemetallating agent to the mixture and thereby metallating thealkenylaminosilane and initiating polymerization of the at least onetype of anionically polymerizable monomer.

A pre-formed metallated aminosilane initiator may be prepared byreacting a metallating agent and at least one compound having formula(IA), (IB), (IIA), or (IIB) in the manner discussed above. At least onetype of anionically polymerizable monomer is then polymerized in thepresence of the metallated aminosilane compound under typicalpolymerization conditions, as discussed below. Also, a metallatedaminosilane initiator may be prepared in situ, in the manner discussedabove, by mixing the metallating agent and alkenylaminosilane compoundwith a solution comprising at least one of the monomers to bepolymerized, and allowing the reaction to proceed by adjusting reactionconditions, as necessary.

The principles of anionic addition polymerization and livingpolymerization are known to those of skill in the art. Anionicallypolymerized polymers may be prepared by either batch, semi-batch orcontinuous methods. In general, a batch polymerization is started bycharging a blend of monomer(s) and solvent to a suitable reactionvessel, followed by the addition of a polar coordinator (if employed)and an initiator compound. The reactants are heated to a suitabletemperature (generally from about 20° C. to about 130° C.) and thepolymerization is allowed to proceed for a sufficient time (generallyfrom about 0.1 to about 24 hours). The reaction produces a polymerhaving a reactive or living end. Unlike a continuous polymerization,initiator is not continuously added to reactor, and reaction product isnot continuously removed.

In a semi-batch polymerization the reaction medium and initiator areadded to a reaction vessel, and the monomer(s) is continuously addedover time at a rate dependent on temperature, monomer/initiator/modifierconcentrations, etc. Unlike a continuous polymerization, the product isnot continuously removed from the reactor.

Generally, in a continuous polymerization reaction, the monomer(s),initiator and solvent are charged as feed streams to a suitable reactionvessel at the same time. Thereafter, a continuous procedure is followedthat removes the product after a suitable residence time. In certainembodiments, additional feed streams may be present to charge additionalcomponents to the reaction vessel, including but not limited to reactionmodifiers, functionalizing agents, terminating agents, and the like. Incertain embodiments, one or more of the feed streams may be combinedprior to charging the reaction vessel, in order to pre-form a component,including but not limited to initiators. In other embodiments, one ormore reactions may be accomplished after the living polymer has beenremoved from the continuous polymerization reactor, including but notlimited to functional termination of the polymer. Additional informationrelating to the principles of continuous polymerization and continuouspolymerization reactors is disclosed in U.S. Pat. Nos. 5,231,152;5,610,227; 6,362,282; 6,451,935; 6,881,795; 6,897,270; and 7,442,748,the disclosures of which are incorporated by reference herein.

The polymerization processes described herein involve at least oneanionically polymerizable monomer and optionally additional comonomers.In general, all known anionically polymerizable monomers may be used.Non-limiting examples of anionically polymerizable monomers includeconjugated dienes and vinyl aromatics, preferably conjugated dieneshaving from 4 to 12 carbon atoms and monovinyl aromatics having from 8to 18 carbon atoms, and more preferably conjugated butadienes andpentadienes, isoprene, myrcene, and styrene.

Anionic polymerizations are typically conducted in a polar solvent, suchas tetrahydrofuran (THF), or a non-polar hydrocarbon, such as thevarious cyclic and acyclic hexanes, heptanes, octanes, pentanes, theiralkylated derivatives, and mixtures thereof, as well as benzene.

In order to promote randomization in copolymerization and to controlvinyl content, a polar coordinator (modifier) may be added to thepolymerization ingredients. The use of polar coordinators is known tothose of skill in the art, and the use of suitable polar coordinators iswithin the scope of this application. Whether to use a polar coordinatorand the amount of modifier to use depends on a number of factors,including but not limited to the amount of vinyl content desired and thetemperature of the polymerization, as well as the nature of the specificpolar coordinator employed. Typically, useful polar coordinators includecompounds having an oxygen or nitrogen heteroatom and a non-bonded pairof electrons. Non-limiting examples include dialkyl ethers of mono andoligo alkylene glycols; “crown” ethers; tertiary amines such astetramethylethylene diamine (TMEDA); and linear THF oligomers.Preferable polar coordinators include but are not limited totetrahydrofuran (THF), linear and cyclic oligomeric oxolanyl alkanessuch as 2,2-bis(2′-tetrahydrofuryl) propane, dipiperidyl ethane,dipiperidyl methane, hexamethylphosphoramide, N,N′-dimethylpiperazine,diazabicyclooctane, dimethyl ether, diethyl ether, tributylamine and thelike. Linear and cyclic oligomeric oxolanyl alkane modifiers aredescribed in U.S. Pat. No. 4,429,091, incorporated herein by reference.

The amount of metallated aminosilane initiator employed in conductingthe anionic polymerizations described herein can vary widely based uponthe desired polymer characteristics. In one embodiment, the metal tomonomer molar ratio may be from 1:10 to 1:20,000. By metal is meant themetal of the metallated aminosilane compound or of the metallatingagent. Likewise, in one embodiment, the metal to alkenylaminosilanecompound or metal to alkylaminosilane compound molar ratio may be from0.8 to 1.2.

In another embodiment of the present application, a telechelic polymeris made by a method comprising the steps of: (a) initiatingpolymerization of at least one type of anionically polymerizable monomerby using an initiator comprising the reaction product of at least onemetallating agent and at least one aminosilane compound having theformula

where n is a whole number selected from the group consisting of 0-2, andm is a whole number selected from the group consisting of 1-3, with theproviso that the sum of m and n equals 3; where X is a methyl, ethyl,propyl, alkenyl, or allylic group; where each R⁷ and R⁸ is independentlya hydrocarbyl group; where each R⁹ is independently a hydrocarbylenegroup; and where one or more R⁸ may form a bridge between two nitrogenatoms when m is greater than 1; (b) propagating the polymerization of atleast one type of anionically polymerizable monomer; and (c) providing afunctional terminator, thereby producing a polymer that includes atleast one aminosilane group at the head of the polymer and at least onefunctional group at the tail of the polymer.

Initiating polymerization of at least one type of anionicallypolymerizable monomer by using the metallated aminosilane initiatordescribed herein and propagating the polymerization are described above.In general, once a desired conversion is achieved, the polymerizationcan be stopped by terminating or coupling. One manner of terminating apolymerization is by protonating the living polymer by adding a compoundthat can donate a proton to the living end. Non-limiting examplesinclude water, and isopropyl and methyl alcohol, and any mixturesthereof.

In one or more embodiments, the living polymer can be terminated with acompound that will impart a functional group to the terminus of thepolymer, thereby causing the resulting polymer to carry at least oneadditional functional group, in addition to the functional groupresulting from use of the initiators described above. Usefulfunctionalizing agents include those conventionally employed in the art.Non-limiting examples of compounds that have been used toend-functionalize living polymers include carbon dioxide, benzophenones,benzaldehydes, imidazolidones, pyrrolidinones, carbodiimides, ureas,isocyanates, and Schiff bases including those disclosed in U.S. Pat.Nos. 3,109,871, 3,135,716, 5,332,810, 5,109,907, 5,210,145, 5,227,431,5,329,005, 5,935,893, which are incorporated herein by reference.Additional examples include trialkyltin halides such as tributyltinchloride, as disclosed in U.S. Pat. Nos. 4,519,431, 4,540,744,4,603,722, 5,248,722, 5,349,024, 5,502,129, and 5,877,336, which areincorporated herein by reference. Other examples include cyclic aminocompounds such as hexamethyleneimine alkyl chloride, as disclosed inU.S. Pat. Nos. 5,786,441, 5,916,976 and 5,552,473, which areincorporated herein by reference. Other examples include N-substitutedaminoketones, N-substituted thioaminoketones, N-substitutedaminoaldehydes, and N-substituted thioaminoaldehydes, includingN-methyl-2-pyrrolidone or dimethylimidazolidinone (i.e.,1,3-dimethylethyleneurea) as disclosed in U.S. Pat. Nos. 4,677,165,5,219,942, 5,902,856, 4,616,069, 4,929,679, 5,115,035, and 6,359,167,which are incorporated herein by reference. Additional examples includecyclic sulfur-containing or oxygen containing azaheterocycles such asdisclosed in U.S. Publication No. 2006/0074197 A1, U.S. Publication No.2006/0178467 A1 and U.S. Pat. No. 6,596,798, which are incorporatedherein by reference. Other examples include boron-containing terminatorssuch as disclosed in U.S. Pat. No. 7,598,322, which is incorporatedherein by reference. Still other examples include cyclic siloxanes suchas hexamethylcyclotrisiloxane, including those disclosed in copendingU.S. Publication No. 2007/0149744 A1, which is incorporated herein byreference. Further, other examples include α-halo-ω-amino alkanes, suchas 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane,including those disclosed in U.S. Publication Nos. 2007/0293620 A1 and2007/0293620 A1, which are incorporated herein by reference. Furtherexamples include γ-mercapto-propyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, and vinylmethyldimethoxy silane. Stillfurther examples include3-bis(trimethylsilyl)aminopropyl-methyldiethoxysilane and3-(1,3-dimethylbutylidene)aminopropyltriethoxysilane. The foregoinglisting of terminating agents is not to be construed as limiting butrather as enabling. While a terminating agent can be employed, practiceof the present invention is not limited to a specific agent or class ofsuch compounds.

In one or more embodiments, the living polymer can be coupled to linktwo or more living polymer chains together. In certain embodiments, theliving polymer can be treated with both coupling and functionalizingagents, which serve to couple some chains and functionalize otherchains. The combination of coupling agent and functionalizing agent canbe used at various molar ratios. Although the terms coupling andfunctionalizing agents have been employed in this specification, thoseskilled in the art appreciate that certain compounds may serve bothfunctions. That is, certain compounds may both couple and provide thepolymer chains with a functional group. Those skilled in the art alsoappreciate that the ability to couple polymer chains may depend upon theamount of coupling agent reacted with the polymer chains. For example,advantageous coupling may be achieved where the coupling agent is addedin a one to one ratio between the equivalents of lithium on theinitiator and equivalents of leaving groups (e.g., halogen atoms) on thecoupling agent. Non-limiting examples of coupling agents include metalhalides, metalloid halides, alkoxysilanes, and alkoxystannanes.

In one or more embodiments, metal halides or metalloid halides may beselected from the group comprising compounds expressed by the formula(1) R^(*) _(n)M¹Y_((4-n)), the formula (2) M¹Y₄, and the formula (3)M²Y₃, where each R* is independently a monovalent organic group having 1to 20 carbon atoms, M¹ is a tin atom, silicon atom, or germanium atom,M² is a phosphorous atom, Y is a halogen atom, and n is an integer of0-3.

Exemplary compounds expressed by the formula (1) include halogenatedorganic metal compounds, and the compounds expressed by the formulas (2)and (3) include halogenated metal compounds.

In the case where M¹ represents a tin atom, the compounds expressed bythe formula (1) can be, for example, triphenyltin chloride, tributyltinchloride, triisopropyltin chloride, trihexyltin chloride, trioctyltinchloride, diphenyltin dichloride, dibutyltin dichloride, dihexyltindichloride, dioctyltin dichloride, phenyltin trichloride, butyltintrichloride, octyltin trichloride and the like. Furthermore, tintetrachloride, tin tetrabromide and the like can be exemplified as thecompounds expressed by formula (2).

In the case where M¹ represents a silicon atom, the compounds expressedby the formula (1) can be, for example, triphenylchlorosilane,trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane,trimethylchlorosilane, diphenyldichlorosilane, dihexyldichlorosilane,dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane,methyltrichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane,octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane andthe like. Furthermore, silicon tetrachloride, silicon tetrabromide andthe like can be exemplified as the compounds expressed by the formula(2). In the case where M¹ represents a germanium atom, the compoundsexpressed by the formula (1) can be, for example, triphenylgermaniumchloride, dibutylgermanium dichloride, diphenylgermanium dichloride,butylgermanium trichloride and the like. Furthermore, germaniumtetrachloride, germanium tetrabromide and the like can be exemplified asthe compounds expressed by the formula (2). Phosphorous trichloride,phosphorous tribromide and the like can be exemplified as the compoundsexpressed by the formula (3). In one or more embodiments, mixtures ofmetal halides and/or metalloid halides can be used.

In one or more embodiments, alkoxysilanes or alkoxystannanes may beselected from the group comprising compounds expressed by the formula(4) R^(*) _(n)M¹(OR̂)_(4-n), where each R* is independently a monovalentorganic group having 1 to 20 carbon atoms, M¹ is a tin atom, siliconatom, or germanium atom, OR̂ is an alkoxy group where R̂ is a monovalentorganic group, and n is an integer of 0-3.

Exemplary compounds expressed by the formula (4) include tetraethylorthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate,tetraethoxy tin, tetramethoxy tin, and tetrapropoxy tin.

An antioxidant may be added along with, before, or after the addition ofthe terminating agent. When the polymerization has been stopped, thepolymer can be recovered from the polymerization mixture by utilizingconventional procedures of desolventization and drying. For instance,the polymer may be isolated from the solution by coagulation of thepolymerization mixture with an alcohol such as methanol, ethanol, orisopropanol, followed by isolation, or by steam distillation of thesolvent and the unreacted monomer, followed by isolation. The isolatedpolymer is then dried to remove residual amounts of solvent and water.Alternatively, the polymer may be isolated from the polymerizationmixture by evaporating the solvent, such as by directly drum drying thepolymerization cement.

In another embodiment of the present application, a polymer compositioncomprises an elastomeric polymer having functionalized chain endsrepresented by the formula

where a and d are whole numbers between 0-2, and b, c, e, and f arewhole numbers between 0-3, with the proviso that the sum of b and c mustbe greater than zero, the sum of e and f must be greater than zero, thesum of a, b, and c equals 3, and the sum of d, e, and f equals 3; whereZ is a hydrocarbyl group having from 1 to 20 carbon atoms; where eachR¹³ is independently a hydrogen or hydrocarbyl group; where each R¹⁰ isindependently an alkyl or aryl group; where each R¹¹ is independently ahydrocarbyl group having between 2 and 12 carbon atoms; where each R¹²is independently a hydrocarbylene group having between 2 and 12 carbonatoms; and where one or more R₁₁ may form a bridge between two nitrogenatoms when b is greater than 1.

The elastomeric polymer of formula (IV) can be made by using analkenylaminosilane compound having formula (IA) or (IB) as a terminatingagent for a living polymer chain that was initiated using a metallatedaminosilane compound comprising the reaction product of a suitablemetallating agent and an alkenylaminosilane compound having formula (IA)or (IB). Generally, a living polymerization reaction may be terminatedusing an alkenylaminosilane compound by introducing thealkenylaminosilane compound to the polymer solution in conjunction withan agent to quench the reaction, such as active hydrogen compounds,including but not limited to water or alcohol.

Suitable metallating agents are described above. Non-limiting examplesof metallating agents include organometallic compounds such ashydrocarbyl lithium compounds, hydrocarbyl sodium compounds, hydrocarbylpotassium compounds, hydrocarbyl magnesium compounds, and combinationsthereof. Preferably, the metallating agent is a hydrocarbyl lithium orhydrocarbyl sodium compound, or combinations thereof. Typically, themetallating agent is a hydrocarbyl lithium compound having the generalformula Z—Li, where Z is selected from the group consisting of alkyls,cycloalkyls, alkenyls, alkynyls, aryls, and aralkyls having from 1 to 20carbon atoms.

Without wishing to be bound by a particular theory, the differingstructure of the functional chain ends of the polymer having formula(IV) results from the fact that different carbon atoms on the alkenylmoeity of alkenylaminosilane compound (IA) or (IB) react with theanionic living polymer, depending on whether the alkenylaminosilane isinvolved with either initiating the polymerization or terminating it. Anon-limiting example of the reaction mechanisms leading to the differingstructure of the functional chain ends is as follows

In another embodiment of the present application, a rubber compositionfor use in tires is provided comprising an aminosilane-functionalizedpolymer made by the processes described previously, at least one rubberypolymer, and at least one filler. In still another embodiment of thepresent application, the aminosilane-functionalized polymer may betelechelic.

The aminosilane-functionalized polymers, and rubber compositionscontaining such functionalized polymers, as described in thisapplication are particularly useful in preparing tire components. Thesetire components may be prepared by using the aminosilane-functionalizedpolymers described in this application alone or together with otherrubbery polymers. The aminosilane-functionalized polymers are formed byinitiating at least one type of anionically polymerizable monomer usinga pre-formed anionic initiator comprising the reaction product of atleast one metallating agent and at least one compound having formula(IA), (IB), (IIA), or (IIB), as described above. In another embodiment,the aminosilane-functionalized polymers are formed by initiating atleast one type of anionically polymerizable monomer using a metallatedaminosilane compound formed in situ, as described above. In anotherembodiment, the aminosilane-functionalized polymers are telechelicpolymers made by using the reaction product of at least one metallatingagent and at least one aminosilane compound having the formula (IIIA) or(IIIB) to initiate polymerization of at least one type of anionicallypolymerizable monomer, as described above, and thereafter terminatingthe polymerization by providing a functional terminator.

Other rubbery polymers that may be used include natural and syntheticelastomers. Non-limiting examples of useful rubbery elastomers includenatural rubber, synthetic polyisoprene, polybutadiene,poly(isobutylene-co-isoprene), neoprene, poly(ethylene-co-propylene),poly(styrene-co-butadiene), poly(styrene-co-isoprene),poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene),poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylicrubber, urethane rubber, silicone rubber, epichlorohydrin rubber, andmixtures thereof. These elastomers can have a myriad of macromolecularstructures including linear, branched and star shaped. Preferredelastomers include natural rubber, polybutadiene, polyisoprene, and thevarious copolymers of styrene, butadiene, and isoprene, because of theircommon usage in the tire industry.

Typically, in the rubber compositions disclosed herein, theaminosilane-functionalized polymer(s) is present in an amount rangingfrom 10 to 100 phr, whereas the other rubbery polymer(s) is present inan amount ranging from 0 to 90 phr.

The rubber compositions may include fillers such as inorganic andorganic fillers, and mixtures thereof. Non-limiting examples of organicfillers include carbon black and starch, and mixtures thereof.Non-limiting examples of inorganic fillers include silica, aluminumhydroxide, magnesium hydroxide, clays (hydrated aluminum silicates), andmixtures thereof.

In one or more embodiments, silica (silicon dioxide) includeswet-process, hydrated silica produced by a chemical reaction in water,and precipitated as ultra-fine spherical particles. In one embodiment,the silica has a surface area of about 32 to about 400 m²/g, in anotherembodiment about 100 to about 250 m²/g, and in yet another embodiment,about 150 to about 220 m²/g. The pH of the silica filler in oneembodiment is about 5.5 to about 7 and in another embodiment about 5.5to about 6.8. Commercially available silicas include Hi-Sil™ 215,Hi-Sil™ 233, Hi-Sil™ 255LD, and Hi-Sil™ 190 (PPG Industries; Pittsburgh,Pa.), Zeosil™ 1165 MP and 175GRPlus (Rhodia), Vulkasil™ (Bary AG),Ultrasil™ VN2, VN3 (Degussa), and HuberSil™ 8745 (Huber).

In one or more embodiments, the carbon black(s) may include any of thecommonly available, commercially-produced carbon blacks. These includethose having a surface area (EMSA) of at least 20 m²/gram and in otherembodiments at least 35 m²/gram up to 200 m²/gram or higher. Surfacearea values include those determined by ASTM test D-1765 using thecetyltrimethyl-ammonium bromide (CTAB) technique. Among the usefulcarbon blacks are furnace black, channel blacks and lamp blacks. Morespecifically, examples of the carbon blacks include super abrasionfurnace (SAF) blacks, high abrasion furnace (HAF) blacks, fast extrusionfurnace (FEF) blacks, fine furnace (FF) blacks, intermediate superabrasion furnace (ISAF) blacks, semi-reinforcing furnace (SRF) blacks,medium processing channel blacks, hard processing channel blacks andconducting channel blacks. Other carbon blacks that may be utilizedinclude acetylene blacks. Mixtures of two or more of the above blackscan be used in preparing the carbon black products of the invention.Exemplary carbon blacks include those bearing ASTM designation(D-1765-82a) N-110, N-220, N-339, N-330, N-351, N-550, and N-660. In oneor more embodiments, the carbon black may include oxidized carbon black.

In one embodiment, silica may be used in an amount of from about 5 toabout 200 parts by weight parts per hundred rubber (phr), in anotherembodiment from about 10 to about 150 parts by weight phr, in yetanother embodiment from about 15 to about 80 parts by weight phr, and instill another embodiment from about 25 to about 75 parts by weight phr.

A multitude of rubber curing agents may be employed, including sulfur orperoxide-based curing systems. Curing agents are described inKirk-Othmer, E NCYCLOPEDIA OF C HEMICAL T ECHNOLOGY, Vol. 20, pgs.365-468, (3^(rd) Ed. 1982), particularly Vulcanization Agents andAuxiliary Materials, pgs. 390-402, and A. Y. Coran, Vulcanization, ENCYCLOPEDIA OF P OLYMER S CIENCE AND E NGINEERING, (2^(nd) Ed. 1989),which are incorporated herein by reference. Vulcanizing agents may beused alone or in combination. In one or more embodiments, thepreparation of vulcanizable compositions and the construction and curingof the tire is not affected by the practice of this invention.

Other ingredients that may be employed include accelerators, oils,waxes, scorch inhibiting agents, processing aids, zinc oxide, tackifyingresins, reinforcing resins, fatty acids such as stearic acid, peptizers,and one or more additional rubbers. Examples of oils include paraffinicoils, aromatic oils, naphthenic oils, vegetable oils other than castoroils, and low PCA oils including MES, TDAE, SRAE, heavy naphthenic oils,and black oils.

These stocks are useful for forming tire components such as treads,subtreads, black sidewalls, body ply skins, bead filler, and the like.Preferably, the functional polymers are employed in tread formulations.In one or more embodiments, these tread formulations may include fromabout 10 to about 100% by weight, in other embodiments from about 35 toabout 90% by weight, and in other embodiments from about 50 to 80% byweight of the functional polymer based on the total weight of the rubberwithin the formulation.

In one or more embodiments, the vulcanizable rubber composition may beprepared by forming an initial masterbatch that includes the rubbercomponent and filler (the rubber component optionally including thefunctional polymer of this invention). This initial masterbatch may bemixed at a starting temperature of from about 25° C. to about 125° C.with a discharge temperature of about 135° C. to about 180° C. Toprevent premature vulcanization (also known as scorch), this initialmasterbatch may exclude vulcanizing agents. Once the initial masterbatchis processed, the vulcanizing agents may be introduced and blended intothe initial masterbatch at low temperatures in a final mix stage, whichpreferably does not initiate the vulcanization process. Optionally,additional mixing stages, sometimes called remills, can be employedbetween the masterbatch mix stage and the final mix stage. Variousingredients including the functional polymer of this invention can beadded during these remills. Rubber compounding techniques and theadditives employed therein are generally known as disclosed in TheCompounding and Vulcanization of Rubber, in Rubber Technology (2^(nd)Ed. 1973).

The mixing conditions and procedures applicable to silica-filled tireformulations are also well known as described in U.S. Pat. Nos.5,227,425, 5,719,207, 5,717,022, and European Patent No. 890,606, all ofwhich are incorporated herein by reference. In one or more embodiments,where silica is employed as a filler (alone or in combination with otherfillers), a coupling and/or shielding agent may be added to the rubberformulation during mixing. Useful coupling and shielding agents aredisclosed in U.S. Pat. Nos. 3,842,111, 3,873,489, 3,978,103, 3,997,581,4,002,594, 5,580,919, 5,583,245, 5,663,396, 5,674,932, 5,684,171,5,684,172 5,696,197, 6,608,145, 6,667,362, 6,579,949, 6,590,017,6,525,118, 6,342,552, and 6,683,135, which are incorporated herein byreference. In one embodiment, the initial masterbatch is prepared byincluding the functional polymer of this invention and silica in thesubstantial absence of coupling and shielding agents. It is believedthat this procedure will enhance the opportunity that the functionalpolymer will react or interact with silica before competing withcoupling or shielding agents, which can be added later curing remills.

Where the vulcanizable rubber compositions are employed in themanufacture of tires, these compositions can be processed into tirecomponents according to ordinary tire manufacturing techniques includingstandard rubber shaping, molding and curing techniques. Any of thevarious rubber tire components can be fabricated including, but notlimited to, treads, sidewalls, belt skims, and carcass. Typically,vulcanization is effected by heating the vulcanizable composition in amold; e.g., it may be heated to about 140 to about 180° C. Cured orcrosslinked rubber compositions may be referred to as vulcanizates,which generally contain three-dimensional polymeric networks that arethermoset. The other ingredients, such as processing aides and fillers,may be evenly dispersed throughout the vulcanized network. Pneumatictires can be made as discussed in U.S. Pat. Nos. 5,866,171, 5,876,527,5,931,211, and 5,971,046, which are incorporated herein by reference.

Additional information relating to the use of fillers, including carbonblack and silica fillers, and additional ingredients in rubbercompositions for use in tire components, and information relating tocompounding such formulations, is disclosed in U.S. Pat. Nos. 7,612,144,6,221,943, 6,342,552, 6,348,531, 5,916,961, 6,252,007, 6,369,138,5,872,176, 6,180,710, 5,866,650, 6,228,908 and 6,313,210, thedisclosures of which are incorporated by reference herein.

The practice of the invention is further illustrated by the followingexamples, which should not be construed as limiting the scope of theinvention as recited in the claims.

General Experimental Testing Procedures

Molecular Weight Determination: Molecular weights were measured by gelpermeation/size exclusion chromatography (SEC) using a Waters Model150-C instrument equipped with a Model 2414 Refractometer and a Model996 Photodiode Array Detector (UV). Molecular weights were calculatedfrom a universal calibration curve based on polystyrene standards andcorrected using the following Mark-Houwink constants for SBR:k=0.000269, α=0.73.

NMR: Styrene and vinyl content, and small molecule structureconfirmation were determined using ¹H-NMR (CDCl₃) and ¹³C NMRmeasurements on a 300 MHz Gemini 300 NMR Spectrometer System (Varian).

Glass Transition Temperature (Tg): The glass transition temperature wasdetermined using a DSC 2910 Differential Scanning calorimeter (TAInstruments). The Tg was determined as the temperature where aninflection point occurred in the heat capacity (Cp) change.

Dynamic Mechanical Properties: The dynamic mechanical properties weremeasured using two techniques. A Rheometrics Dynamic Analyzer RDAII(Rheometric Scientific) in the parallel plate mode was used with 15 mmthick, 9.27 mm diameter buttons. The loss modulus, G″, storage modulus,G′, and tan δ were measured over deformation of 0.25-14.5% γ at 1 Hz and50° C. The Payne Effect was estimated by calculating the difference ofG′ (0.25% γ)−G′ (14.0% γ). A RDA700 (Rheometric Scientific) in thetorsion rectangular mode was also used with samples having thedimensions 31.7 mm×12.7 mm×2.0 mm. The temperature was increased at arate of 5° C. min⁻¹ from −80° C. to 100° C. The moduli (G′ and G″) wereobtained using a frequency of 5 Hz and a deformation of 0.5% γ from −80°C. to −10° C. and 2% γ from −10° C. to 100° C.

Mooney Viscosity: Mooney viscosity measurements were conducted accordingto ASTM-D 1646-89.

EXAMPLES Representative Alkylaminosilane Compound Example 1

Bis-(dimethylamino)phenylmethylsilane was treated with sec-butyllithium(s-BuLi) to effect lithiation, in the manner below, providing a compoundhaving structure A:

The following ingredients were charged to a 300 mL, dry, nitrogen-purgedbottle fitted with a crown seal and nitrile cap liner:bis-(dimethylamino) phenylmethylsilane, 9.23 mmol (2.0 mL, 1.92 g);triethylamine, 5.0 mL; sec-butyllithium, 10.1 mmol (7.2 mL of 1.4Msolution in cyclohexane). The resulting solution was agitated for 2.5hrs at 50° C., and was estimated to be approximately 0.65M in compoundA.

Example 2

The freshly metallated reagent of Example 1 was used to polymerize1,3-butadiene in a sealed bottle. A polymer of M_(n)=25 kg/mol wastargeted. An 800 mL bottle (dried, purged, and fitted as in Example 1)was charged with 31.4 g of 1,3-butadiene in 261 g of anhydrous hexanes,and 2.0 mL (ca. 1.3 mmol) of the reagent of Example 1 was then injectedinto the bottle. The bottle was agitated at 50° C. for 75 min, thenallowed to cool to room temperature overnight. The resulting cement wasquenched with 2 mL of 2-propanol (i-PrOH), and stabilized withdi-t-butyl-p-cresol (DBPC). From the solids content, a conversion of 90%was estimated. The cement was coagulated in ethanol, and the coagulatewas re-dissolved in hexanes, then re-coagulated twice more in the samemanner. The coagulated polymer was dried at room temperature under astream of nitrogen for four hrs, then under vacuum at ca. 70° C.overnight. The polybutadiene (PBD) product had M_(n)=26.9 kg/mol asdetermined by SEC. NMR (¹³C) analysis of the product showed nearlyquantitative incorporation of the silyl group (the ratio of carbons inthe Si—CH ₂ region (11.612.04 ppm) to those from terminal CH₃ (trans,18.1 ppm; cis, 13.0 ppm) was nearly 1:1).

Examples 3-5

Another freshly metallated reagent was prepared as in Example 1 and usedto polymerize 1,3-butadiene and mixtures of styrene and 1,3-butadiene insealed bottles. The polymerization procedure and workup of Example 2 wasfollowed, except that the time of the polymerizations was 120 min. Thesepolymerizations targeted a 125 kg/mol PBD (Example 3: found M_(n)=139.2kg/mol), and 25 and 125 kg/mol styrene-butadiene copolymers (SBRs)(found M_(n)=35.6 and 211.1 kg/mol, Examples 4 and 5, respectively). Thepolymerizations of Examples 3, 4 and 5 proceeded in conversions of 80%,97% and 96%, respectively.

Example 6 Pre-Mixed, Batch

A solution in hexanes of the freshly lithiated reagent ofbis-(dimethylamino)phenylmethylsilane of approximate concentration 0.65Mwas prepared as in Example 1. It was used to initiate copolymerizationof styrene with 1,3-butadiene with target M_(n)=120 kg/mol, in a batchreactor under anhydrous nitrogen atmosphere, according to the followingprocedure. A stirred, 7.6-L autoclave-type reactor was charged with 3755g of anhydrous hexanes, 551.1 g of anhydrous 1,3-butadiene, 129.3 g ofanhydrous styrene, and 1.2 mL of a 1.60M solution of oligomeric oxolanylpropanes in hexanes. The mixture was held at a steady temperature of 49°C., and 8.72 mL (5.67 mmol) of the lithiatedbis-(dimethylamino)phenylmethylsilane solution was added. After reachinga peak temperature of 55.2° C., the polymerization was allowed tocontinue for an additional 60 min, reaching 92% conversion, as estimatedfrom the solids content of the cement. Samples of the product cementwere collected through a needle into dried, purged, sealed 800 mLbottles. Each was quenched with 2 mL of nitrogen-sparged 2-propanol andstabilized with DBPC, and thereafter coagulated in 2-propanol containingadded DBPC. The combined coagulates were drum-dried on a two-roll millat 110° C., yielding Sample No. 6. Properties are summarized in TABLE 1,below.

Example 7 Pre-Mixed, Semi-Batch

Copolymerization of styrene with 1,3-butadiene was carried out undermetered, semi-batch conditions in a stirred batch reactor with anhydrousnitrogen atmosphere, according to the following procedure, with targetM_(n)=140 kg/mol. A stirred, 7.6 L autoclave-type reactor was chargedwith 1710 g of anhydrous hexanes and 0.27 mL of a 1.60M solution ofoligomeric oxolanyl propanes in hexanes. The mixture was heated to andheld at 85° C. Then a mixture of 217.7 g of anhydrous styrene and 462.7g of anhydrous 1,3-butadiene in 2063.4 g of anhydrous hexanes was addedto the reactor at approximately 36 g/min, by use of a meter. After aboutten minutes of metering, 7.48 mL (4.86 mmol) of the 0.65M lithiatedbis-(dimethylamino)phenylmethylsilane solution (prepared freshlyaccording to Example 1) was added. Metered addition of monomers wascontinued for 62 min after charging initiator. Then, samples of theproduct cement were collected through a needle into ten dried, purged,sealed 800 mL bottles. A conversion in the polymerization of 87.4% wasestimated from the solids content of the cement. The cements in five ofthe bottles were quenched, stabilized, coagulated and dried as inExample 6, yielding Sample 7. Properties are summarized in TABLE 1,below.

Example 8 Pre-Mixed, Semi-Batch

The cements in the remaining five bottles of Example 7 were each treatedwith a solution of 0.2M SnCl₄ at 0.6 equiv. of Sn—Cl per Li, and thenagitated at 50° C. for 35 min. After agitation, the cements werequenched, stabilized, coagulated and dried as in the above Examples, toyield Sample 8. Properties are summarized in TABLE 1, below.

Example 9 Pre-Mixed, Batch

The procedure of Example 6 was repeated. The polymerization proceeded at93.4% conversion. The product was worked up as in Example 6, to yieldSample 9, whose properties are included in TABLE 1, below.

Comparative Example A Batch Control

The procedure of Example 6 was followed, with the exception that n-butyllithium was the only initiator. The polymerization proceeded at 96.6%conversion. The product was worked up as in Example 6, to yield Sample10, whose properties are included in TABLE 1, below. Sample A was used acontrol batch polymer for comparative examples.

Comparative Example A′ Batch Control

The procedure of Comparative Example A was followed, yielding a polymerwith very similar properties, designated as Sample A′, whose propertiesare included in TABLE 1, below. Sample A′ also was used as a controlbatch polymer for comparative examples.

Comparative Example B Semi-Batch Control

The metered, semi-batch polymerization procedure of Example 7 wasfollowed, with the exception that n-butyl lithium was the onlyinitiator. The extent of conversion was not measured. The product wasworked up as in Example 6, to yield Sample B, whose characterization isincluded in TABLE 1, below. Sample B was used as a control semi-batchpolymer for comparative examples.

TABLE 1 Sample SEC (THF) ¹H NMR No. Mn (kg/mol) PDI % Cplg % Sty % BlockSty %1,2 %1,2 (BD = 100) Tg° C. (DSC, Mdpt) 6 131 1.05 nil 21.6 1.2 41.352.7 −35.4 7 168.6 1.25 ca. 9 35.5 6.7 12.1 18.7 −47.8 8 212.3 2.1439.2  ″ ″ ″ ″ ″ 9 140.7 1.06 1.6 20.9 1   43.9 55.6 −33   A 117.1 1.030.5 20.1 1.2 44   55   −34.8 A′ 114.2 1.04 nil na na na na −35.1 B 176.71.17 <9   35.3 4.3 12.5 19.2 −43.9

Although the examples shown above used initiator A, reagents withsimilar effectiveness can be generated in a similar fashion from othersubstrates. For example, a lithiated species generated by treatment ofbis-(hexamethyleneimino)octylmethylsilane with sec-butyllithium was usedto initiate polymerization of 1,3-butadiene and copolymerization of1,3-butadiene and styrene (as in Examples 2 and 4 above), producingpolymers in 86% and 97.6% conversion, respectively. Targeting amolecular weight of 25 kg/mol in each case, the products obtained hadM_(n) by SEC of 30.5 and 33.2 kg/mol, respectively. Therefore, a rangeof other structures are effective as well.

In summary, the anionic copolymerizations of 1,3-butadiene and styreneemploying A as initiator proceeded at high conversion to produce highmolecular weight elastomers. The products were obtained at molecularweights at or near those targeted. The polymers incorporate silicon atthe head group, with Si bonded to the polymer chain through a carbonatom.

The polymers were subsequently compounded with other ingredients toprepare vulcanizable elastomeric compounds, using an “all silica”formulation. Component parts by weight, per 100 parts of rubber (phr)are set forth in TABLE 2, below.

TABLE 2 Ingredient Amount (phr) Masterbatch Stage Test rubber 80 Naturalrubber 20 Silica 52.5 Oil 10.0 Stearic acid 2.0 Wax 2.0 Antioxidant 0.95Remill Stage Silica 2.5 Silane coupling agent 5.0 Final Stage Sulfur1.50 Curatives 4.1 Zinc oxide 2.50 Total 183.05

First, the polymer was placed in a 65-g Brabender mixer, and after 0.5minutes, the remaining ingredients except the stearic acid were added.The stearic acid was then added after 3 minutes. The initial componentswere mixed for 5.5 minutes. At the end of mixing the temperature wasapproximately 165° C. Each sample was transferred to a mill operating ata temperature of 60° C., where it was sheeted and subsequently cooled toroom temperature. The mixtures were re-milled for 3.5 minutes at 130°C., whereby coupling agents were added under milder conditions thanthose of the masterbatch stage. Each sample was again transferred to a60° C. mill, sheeted, and cooled to room temperature. The finalcomponents were mixed by adding the remilled mass and the curativematerials to the mixer simultaneously. The initial mixer temperature was65° C., while operating at 45 rpm. The final material was removed fromthe mixer after 2.5 minutes when the material temperature was between100° C. and 105° C. The finals were sheeted into Dynastat buttons and15×15×0.1875 cm sheets. The samples were cured at 171° C. for 15 minutesin standard molds placed in a hot press.

The results of compounded evaluations of the test samples andcomparative samples are summarized in TABLE 3, below.

TABLE 3 Temp. Sweep Strain Sweep (60° C., Polymer (60° C., 2% γ, Ex.Sample ML1 + 4 Dynastat 5% γ, 10 Hz) 10 Hz) No. No. (130° C.) tanδ, 60°C. tanδ ΔG′ (MPa) tanδ 10 A′ 14.2 0.1246 0.1446 4.7647 0.1347 11 6 200.1120 0.1368 4.8560 0.1222 12 A′ 18.9 0.1166 0.1564 4.3799 0.1381 13 624.3 0.1118 0.1380 4.3526 0.1135 14 A′ 15.4 0.1272 0.1558 4.4209 0.134815 9 23.9 0.1076 0.1382 4.0547 0.1031 16 B 49.8 0.1077 0.1400 5.50290.1267 17 7 74.6 0.1040 0.1375 4.8070 0.1207 18 8 92.1 0.1137 0.13784.0719 0.1175

The data in TABLE 3 show appreciable reductions in hysteresis at 60° C.for compounds prepared with elastomers using initiator A, when judgedagainst the comparative examples which used n-butyl lithium initiator.The hysteresis reductions were greater among the polymers made underbatch polymerization conditions (Samples 6 and 9), rather than undersemi-batch conditions (Samples 7 and 8).

Representative Alkenylaminosilane Compound Examples 18-20

Bis-(dimethylamino)ethenylmethylsilane, a compound having structure Babove, was incorporated into polybutadienes (PBD's) in several ways viapolymerizations in 300 mL bottles: (1) by treatment with n-BuLi and usedas an initiator (Example 18, “pre-made” initiator); (2) by adding to apolymerization mixture before initiation (Example 19, “in-situ”); and(3) by adding to a recently-initiated polymerization (Example 20,“post-initiation”). NMR (¹H) analyses of extracted products detected thepresence of bound silyl moieties. Based on the relative areas of theolefinic protons (4.55-6.33 ppm) to those in the Si—CH ₃ region(0.06-0.11 ppm), molecular weights of 24.2, 34.6, and 23.6 kg/mol wereestimated for polymers that were found by GPC to have M_(n)'s of 20.4,22.0, and 21.6 kg/mol, made by the three respective methods above. Thissuggested that a significant amount of the silane was incorporated intothe polymer structures.

Example 21 In Situ, Batch

The procedure for Sample A was repeated. However, this time 1.0 mL ofneat bis(dimethylamino)ethenylmethylsilane was added to the reactoralong with the oligomeric oxolanyl propanes. The temperature peaked at52.8° C. and polymerization proceeded for another 88 minutes thereafter,and reached 93.1% conversion. The cement was collected in 800 mLbottles, which were each quenched with 2 mL of nitrogen-sparged ethanol,and stabilized with DBPC, and thereafter coagulated in 2-propanolcontaining added DBPC. The combined coagulates were drum-dried on atwo-roll mill at 110° C., yielding Sample 21, whose properties areincluded in TABLE 4, below.

Example 22 Pre-Mixed, Batch

The procedure for Sample A was repeated again. However, this time 1.0 mLof neat bis(dimethylamino)ethenylmethylsilane was mixed with 3.34 mL of1.6M n-BuLi and diluted to 50 mL with anhydrous hexanes, and theresulting mixture was charged immediately to the reactor. Thetemperature peaked at 53.3° C. and polymerization proceeded for another60 minutes thereafter, and reached 92% conversion. The cement wascollected in 800 mL bottles, which were each quenched with 2 mL ofnitrogen-sparged ethanol and stabilized with DBPC, and thereaftercoagulated in 2-propanol containing added DBPC. The combined coagulateswere drum-dried on a two-roll mill at 110° C., yielding Sample 22, whoseproperties are included in TABLE 4, below.

Example 23 Post-Initiation, Batch

The procedure for Sample A was repeated again. However, this time 1.0 mLof neat bis(dimethylamino)ethenylmethylsilane was diluted to 25 mL withanhydrous hexanes, and then charged to the reactor two minutes after then-BuLi initiator had been charged. The temperature peaked at 53.3° C.and polymerization proceeded for another 60 minutes thereafter, andreached 92.5% conversion. The cement was collected in 800 mL bottles,which were each quenched with 2 mL of nitrogen-sparged ethanol andstabilized with DBPC, and thereafter coagulated in 2-propanol containingadded DBPC. The combined coagulates were drum-dried on a two-roll millat 110° C., yielding Sample 23, whose properties are included in TABLE4, below.

Comparative Sample C Control Semi-Batch

Copolymerization of styrene with 1,3-butadiene was carried out undermetered, semi-batch conditions in a stirred batch reactor with anhydrousnitrogen atmosphere, according to the following procedure, with targetM_(n)=140 kg/mol. A stirred, 7.6 L autoclave-type reactor was chargedwith 1710 g of anhydrous hexanes and 0.27 mL of a 1.60M solution ofoligomeric oxolanyl propanes in hexanes. The mixture was heated to andheld at 93.3° C. Then a mixture of 217.7 g of anhydrous styrene and462.7 g of anhydrous 1,3-butadiene in 2063.4 g of anhydrous hexanes wasadded to the reactor at approximately 36 g/min, by use of a meter. Afterabout ten minutes of metering, 2.86 mL (4.86 mmol) of 1.6M n-BuLidiluted with 25 mL of anhydrous hexanes was charged to the reactor.Metered addition of monomers was continued for 62 min after charginginitiator, then samples of the product cement were collected through aneedle into dried, purged, 800 mL sealed bottles. The cements in thebottles were each quenched, stabilized, coagulated and dried as forSample A, yielding Sample C. Properties are summarized in TABLE 4,below.

Example 24 Pre-Mixed, Semi-Batch

The procedure for Sample C was followed. However, the initiator used inthis case consisted of a mixture of 6.25 mL of 0.74Mbis(dimethylamino)ethenylmethylsilane in hexanes and 3.15 mL of 1.6Mn-BuLi, which was diluted to 25 mL with anhydrous hexanes. The initiatorwas charged to the reactor immediately after mixing. Peak polymerizationtemperature was attained and the metering was stopped 61 minutesthereafter. As above, the product cement was collected into 800 mLbottles, and each was quenched, stabilized, coagulated and dried as forSample C, yielding Sample 24. Properties are summarized in TABLE 4,below.

TABLE 4 Sample SEC (THF) ¹H NMR No.

A 117.1 1.03 0.5 20.1 1.2 44 55 −34.8 C 165.4 1.2 7.2 34.7 5 11.8 18.1−46.6 21 137.0 1.57 36.3 20.6 1.2 42.5 55.5 −33.9 22 132.3 1.35 25.120.2 1.2 43.2 55.9 −32.7 23 161.2 1.55 41.4 20.9 1.4 43.5 56.7 −32.1 24144.4 1.29 18.7 34.8 5.4 11.7 17.9 −46.1

indicates data missing or illegible when filed

The polymers were subsequently compounded with other ingredients toprepare vulcanizable elastomeric compounds, using an “all silica”formulation, as described in relation to TABLE 2, above. The results ofcompounded evaluations of the test samples and comparative samples aresummarized in TABLE 5, below.

TABLE 5 Temp. Sweep Strain Sweep (60° C., Polymer (60° C., 2% γ, Ex.Sample ML1 + 4 Dynastat 5% γ, 10 Hz) 10 Hz) No. No. (130° C.) tanδ, 60°C. tanδ ΔG′ (MPa) tanδ A A 14.2 0.1262 0.1546 4.6358 0.1348 25 21 57.30.1026 0.1110 1.4385 0.1031 26 22 71.7 0.0977 0.1089 1.7500 0.0966 27 2381.7 0.0104 0.1181 1.8345 0.1009 C C 53.2 0.1153 0.1522 4.8471 0.0966 2824 60.4 0.0784 0.0964 1.6306 0.0722

The data in TABLE 5 show consistent improvements in hysteresisproperties for polymers that incorporate an alkenylaminosilane per themethods described herein.

Additional Examples Using Metallated Aminosilane Initiators

Additional aminosilane compounds were prepared in order to furtherevaluate the use of aminosilanes as initiators.

Example 29 Pre-Mixed, Batch

The procedure for Sample A was utilized to generate styrene-butadienecopolymer. However, this time 1.0 mL of neatdimethylaminodimethylethenylsilane (structure C above) was mixed with3.34 mL of 1.6M n-BuLi and diluted to 50 mL with anhydrous hexanes, andthe resulting mixture was charged immediately to the reactor. Thetemperature peaked at 58.9° C. and polymerization proceeded for another60 minutes thereafter, and reached 94% conversion. The cement wascollected in 800 mL bottles, which were each quenched with 2 mL ofnitrogen-sparged ethanol and stabilized with DBPC, and thereaftercoagulated in 2-propanol containing added DBPC. The combined coagulateswere drum-dried on a two-roll mill at 110° C., yielding Sample 29, whoseproperties are included in TABLE 6, below.

Example 30 Pre-Mixed, Batch

The procedure for Sample A was utilized to generate styrene-butadienecopolymer. However, this time 1.0 mL of neatbis-(hexamethylimino)methylethenylsilane (structure D above) was mixedwith 3.34 mL of 1.6M n-BuLi and diluted to 50 mL with anhydrous hexanes,and the resulting mixture was charged immediately to the reactor. Thetemperature peaked at 57.2° C. and polymerization proceeded for another60 minutes thereafter, and reached 93% conversion. The cement wascollected in 800 mL bottles, which were each quenched with 2 mL ofnitrogen-sparged ethanol and stabilized with DBPC, and thereaftercoagulated in 2-propanol containing added DBPC. The combined coagulateswere drum-dried on a two-roll mill at 110° C., yielding Sample 30, whoseproperties are included in TABLE 6, below.

Example 31A Lithiated Initiator Workup

Tris-(dimethylamino)methylsilane (structure E above) was treated withsec-butyllithium (s-BuLi) to effect lithiation. The followingingredients were charged to a 300 mL, dry, nitrogen-purged bottle fittedwith a crown seal and nitrile cap liner:tris-(dimethylamino)methylsilane, 9.7 mmol (2.0 mL, 1.92 g);triethylamine, 4.0 mL; sec-butyllithium, 10.1 mmol (7.8 mL of 1.3Msolution in cyclohexane). The resulting solution was agitated for 2 hrsat 50° C., and was estimated to be approximately 0.73M in lithiatedreagent.

Example 31B Pre-Mixed, Batch

The procedure for Sample A was utilized to generate styrene-butadienecopolymer. However, this time lithiated tris-(dimethylamino)methylsilane(structure E) was used as the initiator, by preparing the lithiatedreagent as in Example 31A and thereafter immediately charging it to thereactor. The temperature peaked at 56.7° C. and polymerization proceededfor another 60 minutes thereafter, and reached 88% conversion. Thecement was collected in 800 mL bottles, which were each quenched with 2mL of nitrogen-sparged ethanol and stabilized with DBPC, and thereaftercoagulated in 2-propanol containing added DBPC. The combined coagulateswere drum-dried on a two-roll mill at 110° C., yielding Sample 31, whoseproperties are included in TABLE 6, below.

Example 32 Pre-Mixed, Batch

The procedure for Sample A was utilized to generate styrene-butadienecopolymer. However, this time 1.14 mL of neattris-(dimethylamino)ethenylsilane (structure F above) was mixed with3.34 mL of 1.6M n-BuLi and diluted to 50 mL with anhydrous hexanes, andthe resulting mixture was charged immediately to the reactor. Thetemperature peaked at 58.3° C. and polymerization proceeded for another60 minutes thereafter, and reached greater than 90% conversion. Thecement was collected in 800 mL bottles, which were each quenched with 2mL of nitrogen-sparged ethanol and stabilized with DBPC, and thereaftercoagulated in 2-propanol containing added DBPC. The combined coagulateswere drum-dried on a two-roll mill at 110° C., yielding Sample 32, whoseproperties are included in TABLE 6, below.

Example 33 Pre-Mixed, Batch

The procedure for Sample A was utilized to generate styrene-butadienecopolymer. However, this time 1.21 mL of neattris-(dimethylamino)allylsilane (structure G above) was mixed with 3.34mL of 1.6M n-BuLi and diluted to 50 mL with anhydrous hexanes, and theresulting mixture was charged immediately to the reactor. Thetemperature peaked at 58.9° C. and polymerization proceeded for another60 minutes thereafter, and reached greater than 90% conversion. Thecement was collected in 800 mL bottles, which were each quenched with 2mL of nitrogen-sparged ethanol and stabilized with DBPC, and thereaftercoagulated in 2-propanol containing added DBPC. The combined coagulateswere drum-dried on a two-roll mill at 110° C., yielding Sample 33, whoseproperties are included in TABLE 6, below.

Example 34 Pre-Mixed, Semi-Batch

The procedure for Sample C was utilized to generate styrene-butadienecopolymer. However, the initiator used in this case consisted of amixture of 6.25 mL of 0.74M dimethylaminodimethylethenylsilane(structure C above) in hexanes and 3.15 mL of 1.6M n-BuLi, which wasdiluted to 25 mL with anhydrous hexanes. The initiator was charged tothe reactor immediately after mixing. Polymerization temperature wasmaintained between about 85° C. to about 95° C., and the metering wasstopped about 120 minutes later. As above, the product cement wascollected into 800 mL bottles, and each was quenched, stabilized,coagulated and dried as for Sample C, yielding Sample 34. Properties aresummarized in TABLE 6, below.

Example 35 Pre-Mixed, Semi-Batch

The procedure for Sample C was utilized to generate styrene-butadienecopolymer. However, the initiator used in this case consisted of amixture of 6 mL of 0.76M bis-(hexamethylimino)methylethenylsilane(structure D above) in hexanes and 2.94 ml, of 1.6M n-BuLi, which wasdiluted to 25 mL with anhydrous hexanes. The initiator was charged tothe reactor immediately after mixing. Polymerization temperature wasmaintained between about 85° C. to about 95° C., and the metering wasstopped about 120 minutes later. As above, the product cement wascollected into 800 mL bottles, and each was quenched, stabilized,coagulated and dried as for Sample C, yielding Sample 35. Properties aresummarized in TABLE 6, below.

Example 36 Pre-Mixed, Semi-Batch

The procedure for Sample C was utilized to generate styrene-butadienecopolymer. However, the initiator used in this case consisted of amixture of 2.0 mL mL of 9.7M tris-(dimethylamino)methylsilane (structureE above), 4 mL of neat triethylamine, and 7.8 mL of 1.3Msec-butyllithium in cyclohexane, which was agitated for 2.5 hrs at 50°C. (−0.73M in lithiated reagent), and thereafter charged to the reactor.Polymerization temperature was maintained between about 85° C. to about95° C., and the metering was stopped about 120 minutes later. As above,the product cement was collected into 800 mL bottles, and each wasquenched, stabilized, coagulated and dried as for Sample C, yieldingSample 36. Properties are summarized in TABLE 6, below.

Example 37 Pre-Mixed, Semi-Batch

The procedure for Sample C was utilized to generate styrene-butadienecopolymer. However, the initiator used in this case consisted of amixture of 0.91 mL of 4.72M tris-(dimethylamino)ethenylsilane (structureF above) in hexanes and 2.65 mL of 1.6M n-BuLi, which was diluted to 25mL with anhydrous hexanes. The initiator was charged to the reactorimmediately after mixing. Polymerization temperature was maintainedbetween about 85° C. to about 95° C., and the metering was stopped about120 minutes later. As above, the product cement was collected into 800mL bottles, and each was quenched, stabilized, coagulated and dried asfor Sample C, yielding Sample 37. Properties are summarized in TABLE 6,below.

Example 38 Pre-Mixed, Semi-Batch

The procedure for Sample C was utilized to generate styrene-butadienecopolymer. However, the initiator used in this case consisted of amixture of 0.96 mL of 4.44M tris-(dimethylamino)allylsilane (structure Gabove) in hexanes and 2.65 mL of 1.6M n-BuLi, which was diluted to 25 mLwith anhydrous hexanes. The initiator was charged to the reactorimmediately after mixing. Polymerization temperature was maintainedbetween about 85° C. to about 95° C., and the metering was stopped about120 minutes later. As above, the product cement was collected into 800mL bottles, and each was quenched, stabilized, coagulated and dried asfor Sample C, yielding Sample 38. Properties are summarized in TABLE 6,below.

TABLE 6 Sample No. Mn (kg/mol) PDI % Cplg Tg ° C. (DSC, Mdpt) 29 121 1.10.6 −32.2 30 113 1.05 2.4 −35.8 31 114 1.05 0.5 −38.6 32 110 1.07 1.6−35.1 33 111 1.03 — −35.4 34 144 1.29 18.7 −46.1 35 132 1.28 7.9 −45.536 166 1.53 94.2 −48.6 37 150 1.22 5.4 −48.3 38 175 1.52 6 −50.3

The copolymers were thereafter compounded with to prepare vulcanizableelastomeric compounds, as disclosed in TABLE 2, above. Testing of thecompounded rubber yielded the results listed in TABLE 7, below.Headgroup analysis of samples 29, 30, and 32 showed approximately 84%,88%, and 91% functionality, respectively.

TABLE 7 Strain Sweep Temp. Sweep Sample ML1 + 4 Tensile Elong (60° C.,5% γ, 10 Hz) (60° C., 2% γ, 10 Hz) Ex. No. No. (130° C.) (MPa) (%) tanδΔG′ (MPa) tanδ Tg (° C.) 39 A 17.6 12.8 333 0.1553 4.31 0.1362 −21.8 4029 24.7 14.3 287 0.1057 1.24 0.1103 −18.9 41 30 35.6 13.7 307 0.09340.65 0.0796 −19.6 42 31 20.0 15.1 380 0.1392 4.37 0.1317 −23.4 43 3244.1 12.5 234 0.0921 0.64 0.0836 −16.8 44 33 16.5 14.5 315 0.1496 4.290.1279 −20.8 45 C 55.8 16.1 380 0.1476 4.38 0.1270 −27.4 46 C 51.8 18.9367 0.1371 5.10 0.1293 −28.1 47 34 59.6 14.3 338 0.1007 1.95 0.0975−25.6 48 35 67.2 13.7 307 0.0858 1.02 0.0754 −22.6 49 36 84.8 13.9 2600.0828 1.52 0.0727 −23.9 50 37 75.3 15.2 366 0.1211 4.17 0.1086 −27.1 5138 84.4 21.1 398 0.1367 4.49 0.1284 −28.0

The data in TABLE 7 show consistent improvements in hysteresisproperties for polymers that incorporate a metallated aminosilaneinitiator per the methods described herein.

Continuous Polymerization Example Example 52

Bis-(dimethylamino)ethenylmethylsilane (structure B above) wasincorporated into poly(styrene-butadiene) copolymer in the followingmanner.

Polymerization was conducted in a 24.6 liter continuous polymerizationreactor with a 25 minute residence time. The reactor was filled withhexane and the jacket temperature was set at 85° C. The followingingredients were metered into the bottom of the reactor:

-   -   1) 6.64 kg/hr styrene/hexane blend (31.8% styrene),    -   2) 14.77 kg/hr butadiene/hexane blend (21.7% butadiene),    -   3) 12.14 kg/hr hexane,    -   4) 0.27 kg/hr oxolanyl alkane modifier/hexane (0.08 M),    -   5) 4.0 cc/hr 1,2-butadiene (13.8%), and    -   6) 0.35 kg/hr initiator/hexane (0.08M lithium).        A stream of n-BuLi in hexane and a stream of        bis-(dimethylamino)ethenylmethylsilane in hexane were combined        upstream of the reactor to form the initiator feed stream, such        that a residence time of about 30 seconds existed prior to the        combined stream entering the reactor. An additional stream of        3.7 kg/hr butadiene/hexane blend (21.7% butadiene) was added at        the midpoint of the reactor to minimize block styrene formation.

Polymer cement was removed at the top of the reactor into a storagevessel. After about 1-1.5 hours of polymerization time, steady state wasachieved with the top temperature of the reactor at 87.2° C. and thebottom temperature at 82.2° C. After another hour of polymerization,samples were taken at the top of the reactor, drum-dried, and had thefollowing properties: ML1+4 (38); t-80 (1.9 sec); 99.7% conversion(GPC); 36% styrene (NMR); and 41% vinyl (NMR).

A control polymer was synthesized in a similar manner to Example 52,with n-butyl lithium used in place of the metallated aminosilaneinitiator. The properties of both polymers are listed below in TABLE 8.

TABLE 8 % Mn % Block (kg/ Sample ML1 + 4 T-80 Sty Sty %1,2 Tg° C. mol)PDI Control 38 2.3 36.2 7.5 41.4 −28.4 106 1.94 Ex. 52 40 2.2 35.9 7.841 −29.1 97.2 2.14

The polymers were subsequently compounded with other ingredients in themanner described above in relation to TABLE 2 to prepare vulcanizableelastomeric compounds, with the exception that 50 phr of test rubber and50 phr of natural rubber were used, instead of the amounts listed inTABLE 2.

The results of compounded evaluations of the Control and Ex. 52 samplesare summarized in TABLE 9, below

TABLE 9 200% ML1 + 4 Mod T_(b) E_(b) tanδ ΔG′ (MPa) Sample (130° C.)(23° C.) (23° C.) (23° C.) (50° C., 10%, 15 Hz) Control 36 7.75 24.2 5110.170 5.97 Ex. 52 64 9.18 21.7 402 0.150 2.77

The data in TABLE 9 show improvement in hysteresis properties, as in thepreceding examples.

Preparation of Semi-Batch SBRs Example 53-A Control

Copolymerization of styrene with 1,3-butadiene was carried out undermetered, semi-batch conditions in a stirred batch reactor with anhydrousnitrogen atmosphere, according to the following procedure, with targetMn=140 kg/mol. A stirred, 7.6 L autoclave-type reactor was charged with1710 g of anhydrous hexanes and 0.27 mL of a 1.60M solution ofoligomeric oxolanyl propanes in hexanes. The mixture was heated to andheld at 93.3° C. Then a mixture of 217.7 g of anhydrous styrene and462.7 g of anhydrous 1,3-butadiene in 2063.4 g of anhydrous hexanes wasadded to the reactor at approximately 36 g/min, by use of a meter. Afterabout ten minutes of metering, 2.86 mL (4.86 mmol) of 1.6M n-BuLidiluted with 25 mL of anhydrous hexanes was charged to the reactor.Metered addition of monomers was continued for about 110 min aftercharging initiator. About 10 minutes after metering was complete, thepolymer cement was coagulated, stabilized (AO) and dried. Coagulationwas achieved using 2-propanol containing added DBPC. Prior tocoagulation, the product cement was quenched with 1 mL nitrogen-sparged2-propanol and stablized with DBPC. Drying was achieved using a drum ona two-roll mill at 110° C. to yield polymer 52.

Information concerning the Mooney Viscosity and stress relaxation time(T-80) of the resulting polymer is provided in Table 10. The stressrelaxation time (T-80) is the length of time it takes from the momentwhen rotor rotation is stopped immediately after measurement of theML1+4 (100° C.) value (the Mooney Viscosity measured at 100° C. inaccordance with ASTM D-1646-96) for the ML1+4 value to decrease 80%.

Example 53-B Control

The procedure for Example 53-A was followed. Information concerning theMooney Viscosity and stress relaxation time (T-80) of the resultingpolymer is provided in Table 10.

Examples 54-65

The procedure for Example 53-A was followed for each of Examples 54-65.However, the initiator used consisted of a mixture of 6.25 mL of 0.74Mbis(dimethylamino) ethenylmethylsilane (BisDMA) in hexanes and 3.15 mLof 1.6M n-BuLi, which was diluted to 25 mL with anhydrous hexanes. Theinitiator was charged to the reactor immediately after mixing, about 10minutes after metering commenced. Metering was complete about 110minutes after the initiator was charged. Product cements were collectedinto 800 mL bottles, and each was quenched, stabilized, coagulated anddried to yield the polymers described as 54-65 in Table 10. As indicatedin Table 10, quenching for each of Examples 54-65 was conducted usingeither a non-functionalized terminator, i.e., 2-propanol (Examples 54and 60) or a functional terminator in the amounts indicated in Table 10(Examples 55-59 and 61-65). When 2-propanol was used for quenching, itwas used according to the procedure provided in Example 53-A. When afunctional terminator was used, it was added to the bottles of livecement (under nitrogen) in the amount provided in Table 10 (equivalentsare equivalents/Li). After addition of the terminator, the bottles wereagitated for 30 minutes at 50° C. The cement was then quenched with 1 mLof nitrogen-sparged 2-propanol. Coagulation was achieved using excess2-propanol containing 2 phr of antioxidant (butylated hydroxytoluene).The coagulated product was isolated and drying was achieved using a drumon a two-roll mill at 110° C. to yield the polymer.

Information concerning the Mooney Viscosity and stress relaxation time(T-80) of the resulting polymers is also provided in Table 10. Thetarget Mn for the polymers of each of Examples 54-65 was 140 kg/mole.

TABLE 10 Mooney Ex. # Type Initiator Terminator Viscosity T-80 53-AControl BuLi 2-propanol 53.3 1.54 53-B Control BuLi 2-propanol 44.2 1.2854 Initiator only BisDMA⁹ 2-propanol 53.5 1.49 55 Initiator-function-BisDMA⁹ DMI¹ (0.9 58.1 1.55 alized terminator equivalents) 56Initiator-function- BisDMA⁹ TEOS² (0.5 175.9 — alized terminatorequivalents) 57 Initiator-function- BisDMA⁹ TEOS² (0.5 171.9 — alizedterminator equivalents) 58 Initiator-function- BisDMA⁹ TTC³ (0.25 174.9— alized terminator equivalents) 59 Initiator-function- BisDMA⁹Dodecylthio- 74.5 2.36 alized terminator azoline (0.9 equivalents) 60Initiator only BisDMA⁹ 2-propanol 53.2 1.49 61 Initiator-function-BisDMA⁹ TOTM⁴ (0.3 119.5 18.4 alized terminator equivalents) 62Initiator-function- BisDMA⁹ NMP⁵ (0.9 54.4 1.50 alized terminatorequivalents) 63 Initiator-function- BisDMA⁹ DEAB⁶ (0.9 50.8 1.46 alizedterminator equivalents) 64 Initiator-function- BisDMA⁹ D3⁷ (0.9 56.71.54 alized terminator equivalents) 65 Initiator-function- BisDMA⁹GPMOS⁸ (0.9 62.9 27.24 alized terminator equivalents)¹dimethylimidazolidinone ²tetraethyl orthosilicate ³tin tetrachloride⁴trioctyltrimellitate ⁵N-methyl pyrrolidone⁶4,4-bis(N,N-diethylamino)benzophenone ⁷hexamethylcyclotrisiloxane⁸3-glycidoxypropyltrimethoxysilane⁹bis(dimethylamino)ethenylmethylsilane

To the extent that the term “includes” or “including” is used in thespecification or the claims, it is intended to be inclusive in a mannersimilar to the term “comprising” as that term is interpreted whenemployed as a transitional word in a claim. Furthermore, to the extentthat the term “or” is employed (e.g., A or B) it is intended to mean “Aor B or both.” When the applicants intend to indicate “only A or B butnot both” then the term “only A or B but not both” will be employed.Thus, use of the term “or” herein is the inclusive, and not theexclusive use. See, Bryan A. Garner, A Dictionary of Modern Legal Usage624 (2d. Ed. 1995). Also, to the extent that the terms “in” or “into”are used in the specification or the claims, it is intended toadditionally mean “on” or “onto.” Furthermore, to the extent the term“connect” is used in the specification or claims, it is intended to meannot only “directly connected to,” but also “indirectly connected to”such as connected through another component or components.

While the present application has been illustrated by the description ofembodiments thereof, and while the embodiments have been described inconsiderable detail, it is not the intention of the applicants torestrict or in any way limit the scope of the appended claims to suchdetail. Additional advantages and modifications will readily appear tothose skilled in the art. Therefore, the application, in its broaderaspects, is not limited to the specific details, the representativeapparatus and method, and illustrative examples shown and described.Accordingly, departures may be made from such details without departingfrom the spirit or scope of the applicant's general inventive concept.

What is claimed is: 1-34. (canceled)
 35. A metallated aminosilanecompound for initiating an anionic polymerization comprising thereaction product of (1) at least one metallating agent; and (2) at leastone alkenylaminosilane compound having the formula

where n is a whole number selected from the group consisting of 0-2, andm is a whole number selected from the group consisting of 1-3, with theproviso that the sum of m and n equals 3; where each R is independentlya hydrogen, alkyl or aryl group; where each R¹ is independently ahydrocarbyl group; where each R² is independently a hydrocarbyl grouphaving between 2 and 12 carbon atoms; where each R³ is independently ahydrocarbylene group having between 2 and 12 carbon atoms; and where oneor more R² may form a bridge between two nitrogen atoms when m isgreater than
 1. 36. The metallated aminosilane compound of claim 35,where the at least one metallating agent is selected from the groupconsisting of hydrocarbyl lithium compounds, hydrocarbyl sodiumcompounds, hydrocarbyl potassium compounds, hydrocarbyl magnesiumcompounds, and combinations thereof.
 37. The metallated aminosilanecompound of claim 35, where the at least one alkenylaminosilane compoundis selected from the group consisting ofalkyleneiminoalkenyldimethylsilane,bis-(alkyleneimino)alkenylmethylsilane,tris-(alkyleneimino)alkenylsilane, aryleneiminoalkenyldimethylsilane,bis-(aryleneimino)alkenylmethylsilane, tris-(aryleneimino)alkenylsilane,diarylaminoalkenyldimethylsilane, bis-(diarylamino)alkenylmethylsilane,tris-(diaryl)alkenylaminosilane, and combinations thereof.
 38. Themetallated aminosilane compound of claim 35, where the at least onealkenylaminosilane compound is selected from the group consisting ofhexamethyleneiminoethenyldimethylsilane,bis-(hexamethyleneimino)ethenylmethylsilane,tris-(hexamethyleneimino)ethenylsilane,diphenylaminoethenyldimethylsilane,bis-(diphenylamino)ethenylmethylsilane,tris-(diphenyl)ethenylaminosilane, diisobutylaminoethenyldimethylsilane,bis-(diisobutylamino)ethenylmethylsilane,tris-(diisobutylamino)ethenylsilane, and combinations thereof.
 39. Themetallated aminosilane compound of claim 35, where the reaction productis generated in the absence of any monomers selected from the groupconsisting of conjugated diene monomers, monovinyl aromatic monomers,and combinations thereof.
 40. A process for producing anaminosilane-functionalized polymer comprising the steps of: (a)providing a pre-formed initiator by preparing the metallated aminosilanecompound of claim 35, and (b) polymerizing at least one type ofanionically polymerizable monomer by using the metallated aminosilanecompound to initiate the polymerization.
 41. The process of claim 40,where the at least one type of anionically polymerizable monomer isselected from the group consisting of conjugated diene monomers andmonovinyl aromatic monomers.
 42. The process of claim 40, where theaminosilane compound is an alkenylaminosilane compound, and where themetal to alkenylaminosilane compound ratio is between 0.8 and 1.2.
 43. Aprocess for producing an aminosilane-functionalized polymer comprisingthe steps of: (a) providing an initiator formed in situ by mixing atleast one type of anionically polymerizable monomer with at least onealkenylaminosilane compound having the formula

where n is a whole number selected from the group consisting of 0-2, andm is a whole number selected from the group consisting of 1-3, with theproviso that the sum of m and n equals 3; where each R is independentlya hydrogen, alkyl or aryl group; where each R¹ is independently ahydrocarbyl group; where each R² is independently a hydrocarbyl grouphaving between 2 and 12 carbon atoms; where each R³ is independently ahydrocarbylene group having between 2 and 12 carbon atoms; and where oneor more R² may form a bridge between two nitrogen atoms when m isgreater than 1; and thereafter (b) adding at least one metallating agentto the mixture, thereby metallating the alkenylaminosilane andinitiating polymerization of the at least one type of anionicallypolymerizable monomer.
 44. The process of claim 43, where the at leastone metallating agent is selected from the group consisting ofhydrocarbyl lithium compounds, hydrocarbyl sodium compounds, hydrocarbylpotassium compounds, hydrocarbyl magnesium compounds, and combinationsthereof.
 45. The process of claim 43, where the at least onealkenylaminosilane compound is selected from the group consisting ofalkyleneiminoalkenyldimethylsilane,bis-(alkyleneimino)alkenylmethylsilane,tris-(alkyleneimino)alkenylsilane, aryleneiminoalkenyldimethylsilane,bis-(aryleneimino)alkenylmethylsilane, tris-(aryleneimino)alkenylsilane,diarylaminoalkenyldimethylsilane, bis-(diarylamino)alkenylmethylsilane,tris-(diaryl)alkenylaminosilane, and combinations thereof.
 46. Theprocess of claim 43, where the at least one alkenylaminosilane compoundis selected from the group consisting ofhexamethyleneiminoethenyldimethylsilane,bis-(hexamethyleneimino)ethenylmethylsilane,tris-(hexamethyleneimino)ethenylsilane,diphenylaminoethenyldimethylsilane,bis-(diphenylamino)ethenylmethylsilane,tris-(diphenyl)ethenylaminosilane, diisobutylaminoethenyldimethylsilane,bis-(diisobutylamino)ethenylmethylsilane,tris-(diisobutylamino)ethenylsilane, and combinations thereof.
 47. Atelechelic polymer made by a method comprising the steps of: (a)initiating polymerization of at least one type of anionicallypolymerizable monomer by using an initiator comprising the reactionproduct of at least one metallating agent and at least one aminosilanecompound having the formula

where n is a whole number selected from the group consisting of 0-2, andm is a whole number selected from the group consisting of 1-3, with theproviso that the sum of m and n equals 3; where X is a methyl, ethyl,propyl, alkenyl, or allylic group; where each R⁷ and R⁸ is independentlya hydrocarbyl group; where each R⁹ is independently a hydrocarbylenegroup; and where one or more R⁸ may form a bridge between two nitrogenatoms when m is greater than 1, (b) propagating the polymerization of atleast one type of anionically polymerizable monomer; and (c) providing afunctional terminator, thereby producing a polymer that includes atleast one aminosilane group at the head of the polymer and at least onefunctional group at the tail of the polymer.
 48. The polymer of claim47, where the initiator is provided in a metal to monomer molar ratio ofbetween 1:10 and 1:20,000, and where the metal to aminosilane compoundratio is between 0.8 and 1.2.
 49. The polymer of claim 47, where the atleast one metallating agent is selected from the group consisting ofhydrocarbyl lithium compounds, hydrocarbyl sodium compounds, hydrocarbylpotassium compounds, hydrocarbyl magnesium compounds, and combinationsthereof, and the at least one aminosilane compound is selected from thegroup consisting of alkyleneiminoalkenyldimethylsilane,bis(alkyleneimino)alkenylmethylsilane, tris(alkyleneimino)alkenylsilane,aryleneiminoalkenyldimethylsilane, bis(aryleneimino)alkenylmethylsilane,tris(aryleneimino)alkenylsilane, diarylaminoalkenyldimethylsilane,bis(diarylamino)alkenylmethylsilane, tris(diarylamino)alkenylsilane,diisobutylaminoalkenyldimethylsilane,bis(diisobutylamino)alkenylmethylsilane,tris(diisobutylamino)alkenylsilane, and combinations thereof.
 50. Thepolymer of claim 47, where X is selected from the group consisting ofmethyl, ethyl, propyl and allyl groups, and where the at least onemetallating agent comprises a first component and a second component,where the first component is a Lewis base, and where the secondcomponent is selected from the group consisting of hydrocarbyl lithiumcompounds, hydrocarbyl sodium compounds, hydrocarbyl potassiumcompounds, hydrocarbyl magnesium compounds, and combinations thereof.51. The polymer of claim 47, where the functional terminator is selectedfrom the group consisting of carbon dioxide, benzophenones,benzaldehydes, imidazolidones, pyrrolidinones, carbodiimides, ureas,isocyanates, Schiff bases, trialkyltin halides, cyclic amino compounds,N-substituted aminoketones, N-substituted thioaminoketones,N-substituted aminoaldehydes, N-substituted thioaminoaldehydes, cyclicsulfur-containing or oxygen containing azaheterocycles, boron-containingterminators, cyclic siloxanes, and α-halo-ω-amino alkanes.
 52. A polymercomposition comprising an elastomeric polymer having functionalizedchain ends represented by the formula

where a and d are whole number between 0-2, and b, c, e, and f are wholenumbers between 0-3, with the proviso that the sum of b and c must begreater than zero, the sum of e and f must be greater than zero, the sumof a, b, and c equals 3, and the sum of d, e, and f equals 3; where Z isa hydrocarbyl group having from 1 to 20 carbon atoms; where each R¹³ isindependently a hydrogen or hydrocarbyl group; where each R¹⁰ isindependently an alkyl or aryl group; where each R¹¹ is independently ahydrocarbyl group having between 2 and 12 carbon atoms; where each R¹²is independently a hydrocarbylene group having between 2 and 12 carbonatoms; and where one or more R₁₁ may form a bridge between two nitrogenatoms when b is greater than
 1. 53. A polymer made by a methodcomprising the steps of: (a) initiating polymerization of at least onetype of anionically polymerizable monomer by using an initiatorcomprising the reaction product of at least one metallating agent and atleast one aminosilane compound having the formula

where n is a whole number selected from the group consisting of 0-2, andm is a whole number selected from the group consisting of 1-3, with theproviso that the sum of m and n equals 3; where X is a methyl, ethyl,propyl, or allylic group; where each R⁷ and R⁸ is independently ahydrocarbyl group; where each R⁹ is independently a hydrocarbylenegroup; and where one or more R⁸ may form a bridge between two nitrogenatoms when m is greater than 1, (b) propagating the polymerization of atleast one type of anionically polymerizable monomer; and (c) quenchingthe polymerization by exposing the living polymer to a proton source.